U.S. patent application number 12/535449 was filed with the patent office on 2010-02-04 for adducts of metathesis polymers and preparation thereof.
Invention is credited to Mark N. Dedecker, Daniel F. Graves, William L. Hergenrother, James H. Pawlow.
Application Number | 20100029850 12/535449 |
Document ID | / |
Family ID | 41609016 |
Filed Date | 2010-02-04 |
United States Patent
Application |
20100029850 |
Kind Code |
A1 |
Pawlow; James H. ; et
al. |
February 4, 2010 |
Adducts Of Metathesis Polymers And Preparation Thereof
Abstract
Adducts of an unsaturated metathesis polymer or interpolymer and
an unsaturated diacid anhydride. A process for producing adducts of
an unsaturated metathesis polymer or interpolymer and unsaturated
diacid anhydride.
Inventors: |
Pawlow; James H.; (Akron,
OH) ; Hergenrother; William L.; (Akron, OH) ;
Dedecker; Mark N.; (North Canton, OH) ; Graves;
Daniel F.; (Canal Fulton, OH) |
Correspondence
Address: |
BRIDGESTONE AMERICAS, INC.
1200 FIRESTONE PARKWAY
AKRON
OH
44317
US
|
Family ID: |
41609016 |
Appl. No.: |
12/535449 |
Filed: |
August 4, 2009 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61085987 |
Aug 4, 2008 |
|
|
|
Current U.S.
Class: |
525/176 |
Current CPC
Class: |
C08G 61/08 20130101;
C08F 8/46 20130101; C08F 283/14 20130101; C08G 2261/1426 20130101;
C08G 2261/3322 20130101; C08F 8/46 20130101; C08G 2261/418
20130101; C08F 283/14 20130101; C08F 8/46 20130101; Y02E 10/20
20130101; C08F 110/14 20130101; C08F 222/06 20130101; C08F 132/06
20130101; F03B 17/02 20130101 |
Class at
Publication: |
525/176 |
International
Class: |
C08L 67/02 20060101
C08L067/02 |
Claims
1. An adduct of an unsaturated metathesis polymer or interpolymer
and an unsaturated diacid anhydride having the formula:
##STR00010## wherein R.sub.1 and R.sub.2 are the same or different,
and are selected from hydrogen or a monovalent organic group,
wherein the adduct is characterized by having a number average
molecular weight (M.sub.n) of from about 1 to about 60 kg/mol, from
about 2 to about 25 double bonds per 100 carbon atoms in the
polymer chain, from about 0.1 to about 33 weight percent of pendant
anhydride groups, based on the adduct, and having a cis content of
greater than 50%.
2. The adduct of claim 1, wherein the number average molecular
weight ranges from about 1 to about 25 kg/mol.
3. The adduct of claim 2, wherein the number average molecular
weight ranges from about 1 to 14 kg/mol.
4. The adduct of claim 3, wherein the number average molecular
weight ranges from about 3 to about 8 kg/mol.
5. The adduct of claim 1, wherein the pendant anhydride groups are
present in an amount ranging from about 1 to about 10 weight
percent.
6. The adduct of claim 5, wherein the pendant anhydride groups are
present in an amount ranging from about 2 to about 10 weight
percent.
7. The adduct of claim 6, wherein the pendant anhydride groups are
present in an amount ranging from about 2 to about 4 weight
percent.
8. The adduct of claim 1, further characterized by having about 6
to about 20 double bonds per 100 carbon atoms
9. The adduct of claim 8, having about 7 to about 18 double bonds
per 100 carbon atoms.
10. The adduct of claim 9, having about 10 to about 16 double bonds
per 100 carbon atoms.
11. The adduct of claim 1, further characterized by having a
polydispersity index of greater than 1 to less than 6.
12. The adduct of claim 1, wherein the unsaturated diacid anhydride
is maleic anhydride.
13. The adduct of claim 1, wherein the unsaturated diacid anhydride
is maleic anhydride, the number average molecular weight ranges
from about 3 to about 8 kg/mol, the pendant anhydride groups are
present in an amount ranging from about 2 to about 10 weight %, the
polydispersity index is greater than 1 to less than 6, and the cis
content is from about 55% to about 70%.
14. The adduct of claim 1, wherein the unsaturated metathesis
polymer or interpolymer is selected from the group consisting of
cyclopentene, cyclooctene, 1,3-cyclooctadiene, 1,5-cyclooctadiene,
1,5,9-cyclododecatriene, or mixtures thereof.
15. The adduct of claim 1, wherein the cis content is from 51% to
99%.
16. The adduct of claim 1, wherein the cis content is from about
52% to about 80%.
17. The adduct of claim 1, wherein the cis content is from about
52% to about 70%.
18. The adduct of claim 1, wherein the cis content is from about
52% to about 65%.
19. The adduct of claim 1, wherein the cis content is from 52% to
65%.
20. The adduct of claim 1, wherein the cis content is from 53% to
60%.
21. The adduct of claim 1, wherein the cis content is from about
55% to about 70%.
22. The adduct of claim 1, wherein the cis content is from 55% to
70%.
23. The adduct of claim 1, wherein the cis content is greater than
about 55%.
24. A process for preparing an adduct of an unsaturated metathesis
polymer or interpolymer and an unsaturated diacid anhydride having
the formula: ##STR00011## wherein R.sub.1 and R.sub.2 are the same
or different, and are selected from hydrogen or a monovalent
organic group, and wherein the polymer is characterized by having a
number average molecular weight (M.sub.n) of from about 1 to about
60 kg/mol, from about 2 to about 25 double bonds per 100 carbon
atoms in the polymer chain, having a cis content of greater than
50%, and from about 0.1 to about 33 weight percent of pendant
anhydride groups, based on the adduct, comprising reacting an
unsaturated metathesis polymer or interpolymer with an amount of
about 0.1 to about 50 weight percent of the anhydride, based on the
polymer.
25. The process of claim 24, wherein the pendant anhydride groups
are present in the adduct in an amount of about 1 to about 10
weight percent.
26. The process of claim 25, wherein the pendant anhydride groups
are present in an amount of about 2 to about 10 weight percent.
27. The process of claim 24, wherein the number average molecular
weight ranges from about 1 to about 14 kg.mol.
28. The adduct of claim 24, wherein the diacid anhydride is maleic
anhydride.
29. The process of claim 24, wherein the adduct has from about 2 to
about 25 double bonds per 100 carbon atoms in the polymer.
30. The process of claim 24, wherein the adduct has a cis content
of about 55% to about 70%.
Description
RELATED APPLICATIONS
[0001] This application claims priority from U.S. Patent
Application Ser. No. 61/085,987 filed Aug. 4, 2008, the entire
disclosure of which is incorporated herein by reference.
BACKGROUND OF THE DISCLOSURE
[0002] Metathesis polymers are known in the prior art. However,
there is a need for adducts of metathesis polymers that have use in
various applications.
SUMMARY OF THE DISCLOSURE
[0003] The present disclosure relates to adducts of unsaturated
metathesis polymerization-produced polymers and an unsaturated
anhydride having the formula shown below:
##STR00001##
[0004] wherein R.sub.1, and R.sub.2 are the same or different, and
are selected from hydrogen or a monovalent organic group. In one or
more embodiments, the monovalent organic groups may include
hydrocarbyl groups or substituted hydrocarbyl groups such as, but
not limited to, alkyl, cycloalkyl, substituted cycloalkyl, aryl,
substituted aryl, aralkyl, alkaryl, with each group having from 1
to 30 carbon atoms. The hydrocarbyl groups may contain heteroatoms
such as, but not limited to, nitrogen, boron, oxygen, silicon,
sulfur, and phosphorus atoms. The adducts are characterized by
having a number average molecular weight (M.sub.n) of from about 1
to about 60 kg/mol, from about 2 to about 25 double bonds per 100
carbon atoms in the polymer chain, and from about 0.1 to about 33
weight percent of pendant anhydride groups, based on the adduct,
and a cis content of greater than 50%.
[0005] In another embodiment, the adducts have a number average
molecular weight (M.sub.n) of about 1 to about 25 kg/mol, and in a
still further embodiment, an M.sub.n of about 1 to 14 kg/mol, and
still further 1-12 kg/mol, and 1-10 kg/mol, and 3-8 kg/mol.
[0006] In one or more embodiments, the adduct contains from about 5
to about 25 double bonds per 100 carbon atoms. In other
embodiments, the adduct contains from about 6 to about 20 double
bonds per 100 carbon atoms, in other embodiments from about 7 to
about 18 double bonds per 100 carbon atoms, and in other
embodiments, the adduct contains from about 10 to about 16 double
bonds per 100 carbon atoms.
[0007] In another embodiment, the adducts have from about 0.1 to
about 33 weight percent of pendant anhydride groups, based on the
adduct. In another embodiment, the adducts have from about 1 to
about 10 weight % pendant anhydride groups, and in another
embodiment, from about 2 to about 10 weight %.
[0008] In another embodiment, the adducts have from 51% to 99% cis
content, in another embodiment from about 52% to about 85% cis
content, in another embodiment from about 52% to about 80% cis
content, in another embodiment from about 52% to about 75% cis
content, in another embodiment from about 52% to about 70% cis
content in still another embodiment from about 52% to about 65% cis
content, and in another embodiment from 53% to 65% cis content, and
in another embodiment from 53% to 60% cis content, in still another
embodiment from about 55% to about 75% cis content, in another
embodiment from about 55% to about 70% cis content, in another
embodiment greater than about 55% cis content, in another
embodiment greater than about 60% cis content, in another
embodiment greater than about 65% cis content, and in another
embodiment greater than about 70% cis content.
DETAILED DESCRIPTION OF THE DISCLOSURE
[0009] The present disclosure relates to adducts of an unsaturated
metathesis polymer and an unsaturated diacid anhydride having the
formula shown below.
##STR00002##
wherein R.sub.1, and R.sub.2 are the same or different, and are
selected from hydrogen or a monovalent organic group. In one or
more embodiments, the monovalent organic groups may include
hydrocarbyl groups or substituted hydrocarbyl groups such as, but
not limited to, alkyl, cycloalkyl, substituted cycloalkyl, aryl,
substituted aryl, aralkyl, alkaryl, with each group having from 1
to 30 carbon atoms. The hydrocarbyl groups may contain heteroatoms
such as, but not limited to, nitrogen, boron, oxygen, silicon,
sulfur, and phosphorus atoms.
[0010] The adducts are characterized by having a number average
molecular weight (M.sub.n) of from about 1 to about 60 kg/mol, from
about 2 to about 25 double bonds per 100 carbon atoms in the
polymer chain, from about 0.1 to about 33 weight percent of pendant
anhydride groups, based on the adduct, and having a cis content of
greater than 50%.
[0011] In another embodiment, the adducts have a number average
molecular weight (M.sub.n) of about 1 to about 25 kg/mol, and in
still further embodiment, an M.sub.n of about 1 to about 14 kg/mol,
and still further, about 1 to about 12 kg/mol, and about 1 to about
10 kg/mol, and about 3 to about 8 kg/mol.
[0012] In one or more embodiments, the adduct contains from about 5
to about 25 double bonds per 100 carbon atoms. In other
embodiments, the adduct contains from about 6 to about 20 double
bonds per 100 carbon atoms, in other embodiments from about 7 to
about 18 double bonds per 100 carbon atoms, and in other
embodiments, the adduct contains from about 10 to about 16 double
bonds per 100 carbon atoms.
[0013] In another embodiment, the adducts have from 51% to 99% cis
content, in another embodiment from about 52% to about 85% cis
content, in another embodiment from about 52% to about 80% cis
content, in another embodiment from about 52% to about 75% cis
content, in another embodiment from about 52% to about 70% cis
content in still another embodiment from about 52% to about 65% cis
content, and in another embodiment from 53% to 65% cis content, and
in another embodiment from 53% to 60% cis content, in still another
embodiment from about 55% to about 75% cis content, in another
embodiment from about 55% to about 70% cis content, in another
embodiment greater than about 55% cis content, in another
embodiment greater than about 60% cis content, in another
embodiment greater than about 65% cis content, and in another
embodiment greater than about 70% cis content.
[0014] In another embodiment, the adducts have from about 0.1 to
about 33 weight percent of pendant anhydride groups, based on the
adduct In another embodiment, the adducts have from about 0.5 to
about 20 weight % pendant anhydride groups, in another embodiment,
from about 2 to about 10 weight %, and in another embodiment from
about 2 to about 8 weight % pendant anhydride groups.
[0015] The adducts may have a polydispersity index of greater than
1 to less than 6. In more detail, any metathesis produced polymer,
including homopolymers and interpolymers, may be utilized in
preparation of the adducts. Metathesis polymers, including
interpolymers, are well known in the prior art. Regardless, the
following is a description of typical known methods for producing
the metathesis polymers.
[0016] The metathesis type polymerization process reaction may be
ring opening metathesis polymerization (ROMP), acyclic diene
metathesis polymerization (ADMET), or the like. In certain
embodiments, high molecular weight unsaturated polymers may be
modified (e.g., molecular weight reduction) by employing metathesis
catalysts to provide unsaturated polymers. A functional olefin
(i.e., an olefin including one or more functional groups) may be
employed to yield unsaturated functional interpolymers or protected
functional interpolymers.
[0017] Any catalyst capable of metathesis polymerization is useful
in practicing the process. In one or more embodiments, the
metathesis catalyst includes a transition metal carbene complex or
a transition metal alkylidene complex. Suitable transition metal
complexes include a positively charged metal center (e.g. in the
+2, +4, or +6 oxidation state) that is penta- or hexa-coordinated.
Exemplary transition metals include transition metals from Groups 3
to 12 of the Periodic Table, according to IUPAC conventions.
[0018] Metathesis catalysts that are also useful include tungsten
and/or molybdenum-based metathesis catalysts. These catalysts
include those that may be formed in situ from salts such as
tungsten salts, and molybdenum and tungsten complexes known as
Schrock's carbenes. Additionally, supported systems can be used,
especially where gas-phase polymerization is employed.
Tungsten-based metathesis catalysts are further described in U.S.
Pat. Nos. 3,932,373, and 4,391,737, and Schrock catalysts are
described in U.S. Pat. Nos. 4,681,956, 5,087,710, and
5,142,073.
[0019] In one or more embodiments, the metathesis catalyst includes
a ruthenium-based or osmium-based metathesis catalyst. Any
ruthenium-based or osmium-based metathesis catalyst that is
effective for metathesis polymerization reactions can be used.
[0020] In one embodiment, the ruthenium-based or osmium-based
metathesis catalysts includes carbene complexes of the type
sometimes referred to as Grubbs catalysts. Grubbs metathesis
catalysts are described in U.S. Pat. Nos. 5,312,940, 5,342,909,
5,831,108, 5,969,170, 6,111,121, 6,211,391, 6,624,265, 6,696,597
and U.S. Published App. Nos. 2003/0181609 A1, 2003/0236427 A1, and
2004/0097745 A9.
[0021] Ru-- or Os-based metathesis catalysts include compounds that
can be represented by the formula
##STR00003##
[0022] where M includes ruthenium or osmium, L and L' each
independently include any neutral electron donor ligand, A and A'
each independently include an anionic substituent, R.sup.3 and
R.sup.4 independently comprise hydrogen or an organic group, and
includes an integer from 0 to about 5, or where two or more of
R.sup.3, R.sup.4, L, L', A, and A' combine to form a bidentate
substituent.
[0023] In one embodiment, L and L' independently include phosphine,
sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine,
stibine, ether, amine, amide, imine, sulfoxide, carboxyl, nitrosyl,
pyridine, thioether, trizolidene, or imidazolidene groups, or L and
L' may together include a bidentate ligand. In one embodiment, L
and/or L' include an imidizolidene group that can be represented by
the formulas
##STR00004##
[0024] where R.sup.5 and R.sup.6 independently include alkyl, aryl,
or substituted aryl. In one embodiment, R.sup.5 and R.sup.6
independently include substituted phenyls, and in another
embodiment, R.sup.5 and R.sup.6 independently include mesityl. In
one embodiment, R.sup.7 and R.sup.8 include alkyl or aryl, or form
a cycloalkyl, and in another embodiment, are both hydrogen,
t-butyl, or phenyl groups. Two or more of R.sup.5, R.sup.6, R.sup.7
and R.sup.8 can combine to form a cyclic moiety. Examples of
imidazolidine ligands include 4,5-dihydro-imidazole-2-ylidene
ligands.
[0025] In one embodiment, A and A' independently include halogen,
hydrogen, C.sub.1-C.sub.20 alkyl, aryl, C.sub.1-C.sub.20 alkoxide,
aryloxide, C.sub.2-C.sub.20 alkoxycarbonyl, arylcarboxylate,
C.sub.1-C.sub.20 carboxylate, arylsulfonyl, C.sub.1-C.sub.20
alkylsulfonyl, C.sub.1-C.sub.20 alkylsulfinyl, each ligand
optionally being substituted with C.sub.1-C.sub.5 alkyl, halogen,
C.sub.1-C.sub.5 alkoxy, or with a phenyl group that is optionally
substituted with halogen, C.sub.1-C.sub.5 alkyl, or C.sub.1-C.sub.5
alkoxy, and A and A' together may optionally include a bidentate
ligand.
[0026] In one embodiment, R.sup.3 and R.sup.4 include groups
independently selected from hydrogen, C.sub.1-C.sub.20 alkyl, aryl,
C.sub.1-C.sub.20 carboxylate, C.sub.1-C.sub.20 alkoxy, aryloxy,
C.sub.1-C.sub.20 alkoxycarbonyl, C.sub.1-C.sub.20 alkylthio,
C.sub.1-C.sub.20 alkylsulfonyl and C.sub.1-C.sub.20 alkylsulfinyl,
each of R.sup.3 and R.sup.4 optionally substituted with
C.sub.1-C.sub.5 alkyl, halogen, C.sub.1-C.sub.5 alkoxy or with a
phenyl group that is optionally substituted with halogen,
C.sub.1-C.sub.5 alkyl, or C.sub.1-C.sub.5 alkoxy.
[0027] In one embodiment, L or L' and A or A' may combine to form
one or more bidentate ligands. Examples of this type of complex are
described as Class II catalysts in U.S. Pat. No. 6,696,597. In
another embodiment, R.sup.3 or R.sup.4 and L or L' or A or A' may
combine to form one or more bidentate ligands. This type of complex
is sometimes referred to as Hoveyda or Hoveyda-Grubbs catalysts.
Examples of bidentate ligands that can be formed by R.sup.3 or
R.sup.4 and L or L' include ortho-alkoxyphenylmethylene
ligands.
[0028] Other useful catalysts include hexavalent carbene compounds
including those represented by the formula
##STR00005##
[0029] where M includes ruthenium or osmium, L, L', L'' each
independently include any neutral electron donor ligand, A, A', and
A'' each independently include an anionic substituent, and R.sup.3
and R.sup.4 independently comprise hydrogen or an organic group. In
a manner similar to the penta-valent catalysts described above, one
or more of the substituents in the hexa-valent complex may combine
to form a bidentate substituent.
[0030] Examples of ruthenium-based carbene complexes include
ruthenium, dichloro(phenylmethylene)bis(tricyclohexylphosphine),
ruthenium, dichloro(phenylmethylene)bis(tricyclopentylphosphine),
ruthenium,
dichloro(3-methyl-2-butenylidene)bis(tricyclohexylphosphine),
ruthenium,
dichloro(3-methyl-2-butenylidene)bis(tricyclopentylphosphine),
ruthenium,
dichloro(3-phenyl-2-propenylidene)bis(tricyclohexylphosphine),
ruthenium,
dichloro(3-phenyl-2-propenylidene)bis(tricyclopentylphosphine),
ruthenium, dichloro(ethoxymethylene)bis(tricyclohexylphosphine),
ruthenium, dichloro(ethoxymethylene)bis(tricyclopentylphosphine),
ruthenium, dichloro(t-butylvinylidene)bis(tricyclohexylphosphine),
ruthenium, dichloro(t-butylvinylidene)bis(tricyclopentylphosphine),
ruthenium, dichloro(phenylvinylidene)bis(tricyclohexylphosphine),
ruthenium, dichloro(phenylvinylidene)bis(tricyclopentylphosphine),
ruthenium,[2-(((2,6-bismethylethyl)-4-nitrophenyl)imino-kN)methyl-4-nitro-
phenolato-kO)]chloro-(phenylmethylene)(tricyclohexylphosphine),
ruthenium,[2-(((2,6-bismethylethyl)-4-nitrophenyl)imino-kN)methyl-4-nitro-
phenolato-kO)]chloro-(phenylmethylene)(tricyclopentylphosphine),
ruthenium,[2-(((2,6-bismethylethyl)-4-nitrophenyl)imino-kN)methyl-4-nitro-
phenolato-kO)]chloro-(3-methyl-2-butenylidene)(tricyclohexylphosphine),
ruthenium,[2-(((2,6-bismethylethyl)-4-nitrophenyl)imino-kN)methyl-4-nitro-
phenolato-kO)]chloro-(3-methyl-2-butenylidene)(tricyclopentylphosphine),
ruthenium,[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene][2-(((2,-
6-bismethylethyl)-4-nitrophenyl)imino-kN)methyl-4-nitrophenolato-kO)]chlor-
o-(phenylmethylene),
ruthenium,[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene][2-(((2,-
6-bismethylethyl)-4-nitrophenyl)imino-kN)methyl-4-nitrophenolato-kO)]chlor-
o-(3-methyl-2-butenylidene), ruthenium,
dichloro[1,3-dihydro-1,3-bis-(2,4,6-trimethylphenyl)-2H-imidazol-2-yliden-
e](phenylmethylene)(tricyclohexylphosphine), ruthenium,
dichloro[1,3-dihydro-1,3-bis-(2,4,6-trimethylphenyl)-2H-imidazol-2-yliden-
e](phenylmethylene)(tricyclopentylphosphine), ruthenium,
dichloro[1,3-dihydro-1,3-bis-(2,4,6-trimethylphenyl)-2H-imidazol-2-yliden-
e](3-methyl-2-butenylidene)(tricyclohexylphosphine), ruthenium,
dichloro[1,3-dihydro-1,3-bis-(2,4,6-trimethylphenyl)-2H-imidazol-2-yliden-
e](3-methyl-2-butenylidene)(tricyclopentylphosphine), ruthenium,
dichloro[1,3-dihydro-1,3-bis-(2,4,6-trimethylphenyl)-2H-imidazol-2-yliden-
e](3-phenyl-2-propenylidene)(tricyclohexylphosphine), ruthenium,
dichloro[1,3-dihydro-1,3-bis-(2,4,6-trimethylphenyl)-2H-imidazol-2-yliden-
e](3-phenyl-2-propenylidene)(tricyclopentylphosphine), ruthenium,
dichloro[1,3-dihydro-1,3-bis-(2,4,6-trimethylphenyl)-2H-imidazol-2-yliden-
e](ethoxymethylene)(tricyclohexylphosphine), ruthenium,
dichloro[1,3-dihydro-1,3-bis-(2,4,6-trimethylphenyl)-2H-imidazol-2-yliden-
e](ethoxymethylene)(tricyclopentylphosphine), ruthenium,
dichloro[1,3-dihydro-1,3-bis-(2,4,6-trimethylphenyl)-2H-imidazol-2-yliden-
e](t-butylvinylidene)(tricyclohexylphosphine), ruthenium,
dichloro[1,3-dihydro-1,3-bis-(2,4,6-trimethylphenyl)-2H-imidazol-2-yliden-
e](t-butylvinylidene)(tricyclopentylphosphine), ruthenium,
dichloro[1,3-dihydro-1,3-bis-(2,4,6-trimethylphenyl)-2H-imidazol-2-yliden-
e](phenylvinylidene)(tricyclohexylphosphine), ruthenium,
dichloro[1,3-dihydro-1,3-bis-(2,4,6-trimethylphenyl)-2H-imidazol-2-yliden-
e](phenylvinylidene)(tricyclopentylphosphine),
ruthenium,[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-dichlor-
o(phenylmethylene)(tricyclohexylphosphine),
ruthenium,[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-dichlor-
o(phenylmethylene)(tricyclopentylphosphine),
ruthenium,dichloro[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-
(3-methyl-2-butenylidene)(tricyclohexylphosphine),
ruthenium,dichloro[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-
(3-methyl-2-butenylidene)(tricyclopentylphosphine),
ruthenium,dichloro[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-
(3-phenyl-2-propylidene)(tricyclohexylphosphine),
ruthenium,dichloro[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-
(3-phenyl-2-propylidene)(tricyclopentylphosphine),
ruthenium,[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-dichlor-
o(ethoxymethylene)(tricyclohexylphosphine),
ruthenium,[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-dichlor-
o(ethoxymethylene)(tricyclopentylphosphine),
ruthenium,[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-dichlor-
o(t-butylvinylidene)(tricyclohexylphosphine),
ruthenium,[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-dichlor-
o(t-butylvinylidene)(tricyclopentylphosphine),
ruthenium,[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-dichlor-
o(phenylvinylidene)(tricyclohexylphosphine), and
ruthenium,[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-dichlor-
o(phenylvinylidene)(tricyclopentylphosphine).
[0031] Commercially available Ru-based metathesis catalysts include
ruthenium, dichloro(phenylmethylene)bis(tricyclohexylphosphine)
(sometimes referred to as Grubbs First Generation Catalyst),
ruthenium,[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro-
(phenylmethylene)(tricyclohexylphosphine) (sometimes referred to as
Grubbs Second Generation Catalyst), ruthenium,
dichloro[[2-(1-methylethoxy)phenyl]methylene](tricyclohexylphosphine),
(sometimes referred to as Hoveyda-Grubbs First Generation
Catalyst), and ruthenium,
[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro[[2,(1-meth-
ylethoxy)phenyl]methylene], (sometimes referred to as
Hoveyda-Grubbs Second Generation Catalyst). These Ru-based
metathesis catalysts are available from Materia Inc. (Pasadena,
Calif.).
[0032] In one embodiment, the Ru-based or Os-based metathesis
catalyst can be prepared in situ. For example, a Ru or Os compound
can be combined with an alkyne and an appropriate ligand under
known conditions to form a metal carbene complex such as those
described above.
[0033] In one or more embodiments, useful olefin monomers include
those that will undergo a metathesis reaction, i.e. those that
include at least one metathesis-active double bond. The
cycloolefins may be a cycloalkene or a cyclopolyene. Suitable
examples of acyclic monomers include dienes, alpha omega dienes,
oligomers of olefins, and the like.
[0034] In certain embodiments, the olefin is a mixture of two or
more different olefins that differ in at least one aspect such as
the number of carbon atoms or heteroatoms and the amount and kind
of substituents. Two or more different olefins may also refer to
two or more olefinic isomers. In one embodiment, the ratio of first
olefin to second olefin is from about 99:1 to 1:99, in another
embodiment from about 95:5 to 5:95, and in yet another embodiment
from about 90:10 to 10:90. In the instance where ROMP is used, the
cycloolefin includes a mixture of two or more cycloolefins that
differ in ring size or in substituents, or a mixture of two or more
isomers of cycloolefins. Any combination of two or more
cycloolefins can be used that provides the desired polymer
properties, as discussed below. In one embodiment, the mixture
includes 1,5-cycloooctadiene and cyclopentene, in other embodiments
1,5-cyclooctadiene and cyclooctene, and in still other embodiments
cyclooctene and cyclopentene. Any cycloolefin that can participate
in a ring-opening metathesis polymerization (ROMP) reaction may be
used. The cycloolefin may include one or more substituent groups
and/or functional groups. The cycloolefin may be a cycloalkene or a
cyclopolyene.
[0035] Cycloolefins include compounds represented by the
formula
##STR00006##
[0036] where z includes an integer from 1 to about 18. Examples of
cycloolefins include cyclopropene, cyclobutene, benzocyclobutene,
cyclopentene, dicyclopentadiene, norbornene, norbornadiene,
cycloheptene, cyclooctene, 7-oxanorbornene, 7-oxanorbornadiene,
cyclodecene, 1,3-cyclooctadiene, 1,5-cyclooctadiene,
1,3-cycloheptadiene, [2.2.1]bicycloheptenes, [2.2.2]bicyclooctenes,
cyclohexenylnorbornenes, norbornene dicarboxylic anhydrides,
cyclododecene, 1,5,9-cyclododecatriene, and derivatives thereof. In
one embodiment, the cycloolefin is cyclopentene, cyclooctene,
1,3-cyclooctadiene, 1,5-cyclooctadiene, 1,5,9-cyclododecatriene, or
mixtures thereof. It will be recognized by those of skill in the
art that the thermodynamics of ring-opening polymerization varies
based upon factors such as ring size and substituents. Ring-opening
metathesis is described in K. J. Irvin and J. C. Mol, Olefin
Metathesis and Metathesis Polymerization, Chap. 11 (1997).
[0037] An acyclic alkene including a functional group may be
present during the polymerization or added to the polymerization
mixture. The functional alkene, which may also be referred to as a
functionalizing agent, includes at least one metathesis-active
double bond. The acyclic alkene includes functional end-groups. The
above may be represented by the formula
##STR00007##
[0038] where Z includes a functional group and n includes an
integer from 0 to about 20. A mixture of two or more functionalized
alpha olefins may be used, and can be represented by the
formula
##STR00008##
[0039] where each Z, which may be the same or different, is a
functional group and n is an integer from 0 to about 20, in another
embodiment, n is an integer from about 1 to about 9, in yet another
embodiment, n is an integer less than about 6. In addition to
providing functionalization, these functional alkenes may also be
used to control the molecular weight of the metathesis polymer
during polymerization.
[0040] In one or more embodiments, the glass transition temperature
of the methathesis polymer is less than -75.degree. C., in another
embodiment less than about -77.degree. C., in another embodiment
less than about -80.degree. C., and in still another embodiment
less than about -85.degree. C.
[0041] The synthetic techniques employed to prepare the metathesis
polymers, including interpolymers, include conventional metathesis
polymerization techniques. These reactions may include ring-opening
metathesis polymerization (ROMP) and/or acyclic diene metathesis
polymerization (ADMET); these reactions are known in the art as set
forth in U.S. Pat. Nos. 5,728,917 and 5,290,895, and 5,969,170.
Metathesis polymers can also be prepared by the metathesis
depolymerization of higher molecular weight unsaturated polymers
(see WO2006/127483 A1). The use of functional alkenes, including
multi-functional alkenes, in metathesis reaction, is also known and
disclosed as U.S. Pat. No. 5,880,231 and U.S. Ser. No.
11/344,660.
[0042] In one or more embodiments, the reactants and catalysts are
introduced in an inert atmosphere. The order of reactant or
catalyst addition is not limited. In one embodiment, two or more
metathesis-active olefin monomers are combined to form a mixture,
and then the metathesis catalyst is added to the mixture. One or
more of the materials may be introduced together with a
solvent.
[0043] Metathesis polymerization reactions typically occur at
temperatures that are below the ceiling temperature of the
monomers. In one embodiment, the metathesis reaction occurs at a
temperature of from minus 40.degree. C. to about 100.degree. C., in
another embodiment, the temperature is from about minus 20.degree.
C. to about 75.degree. C., in yet another embodiment, the
temperature is from about 0.degree. C. to about 55.degree. C.
[0044] The progress of the reaction can optionally be monitored by
standard analytical techniques. The metathesis reaction may
optionally be terminated by adding a catalyst deactivator, such as
ethyl vinyl ether.
[0045] After reaction, the metathesis-polymerized polymer may be
isolated from the solvent using conventional procedures. In one or
more embodiments, especially where the functional groups are
sensitive to water, known techniques can be used to prevent or
diminish contact with water.
[0046] In producing a polymer, the amount of monomer(s) and
optionally acyclic alkene, that are employed in the metathesis
reaction is not particularly limited. Advantageously, the molar
ratio of the acyclic alkene to the monomers can be selected to
adjust the molecular weight of the polymer. For example, a
molecular weight of about 1 kg/mol to about 10 kg/mol can be
obtained when the molar ratio of acyclic alkene to the monomers is
from about 1:9 to about 1:150.
[0047] For polymerization of interpolymers, the relative amount of
each monomer is not limited. In one embodiment, the ratio of first
monomer to second monomer is from about 99:1 to about 1:99, in
another embodiment, the ratio of first monomer to second monomer is
from about 95:5 to about 5:95, in yet another embodiment, the ratio
of first monomer to second monomer is from about 90:10 to about
10:90.
[0048] The amount of metathesis catalyst employed in the metathesis
reaction is not critical, however a catalytic amount of catalyst is
typically employed. In one embodiment, the amount of catalyst is at
least about 0.1 mmol catalyst per 100 moles olefin, in other
embodiments at least about 1 mmol catalyst per 100 moles olefin, in
other embodiments, the amount of catalyst is from about 5 mmol to
about 10 moles catalyst per 100 moles olefin, and still other
embodiments from about 10 mmol to about 1 moles catalyst per 100
moles olefin, and yet another embodiment about 0.02 to about 0.5
moles catalyst per 100 moles olefin. In other embodiments,
metathesis catalysis can be employed in conjunction with existing
high molecular weight metathesis polymers to form the desired
polymers of this invention. In other words, metathesis catalysis
can be employed to prepare polymer of a desired molecular weight by
introducing the catalyst to unsaturated high molecular weight
polymer and acyclic alkene. The high molecular weight polymer that
can be used in this process includes high molecular weight polymer
produced by metathesis polymerization. For example, high molecular
weight polymer resulting from the polymerization of cyclooctene
having a molecular weight of about 90 kg/mole, less than 1% pendant
vinyl, and about 12 to about 15 double bonds per 100 carbon atoms
in the polymer chain are commercially available under the tradename
Vestenamer.TM. (Degussa). These polymers can be contacted with a
metathesis catalyst and an acyclic alkene to produce a lower
molecular weight metathesis polymer. Also, by employing
functionalized acyclic alkenes, the resulting metathesis polymer
can be end-functionalized. Optionally, a cycloolefin or diene
containing a metathesis-reactive double bond can be added to
copolymerize with the base polymer and thereby form an interpolymer
having at least one or more terminal functional groups.
[0049] The unsaturated metathesis polymer used herein has a Mn of
about 1 to about 40 kg/mol, and has about 2 to about 25 double
bonds per 100 carbon atoms. The polymers may have a polydispersity
index of greater than 1 to less than 6. In one embodiment, the
polymers may have a cis content of about greater than 51%, or from
about 55% to about 70% or greater than about 55%.
[0050] Any of the metathesis polymers including homopolymers or
interpolymers may be utilized in producing adducts herein. The
metathesis polymers or interpolymers adducted from about 0.1 to
about 33 weight % unsaturated diacid anhydride are characterized by
having a number average molecular weight (M.sub.n) of about 1 to
about 60 kg/mol, and about 2 to about 25 double bonds per 100
carbon atoms in the polymer chain. The adducts may have a
polydispersion index of greater than 1 to less than 6.
[0051] In another embodiment, the adducts have a number average
molecular weight (M.sub.n) of about 1 to about 25 kg/mol, and in a
still further embodiment, an M.sub.n of about 1 to about 14 kg/mol,
and further yet, an M.sub.n of about 1 to about 12, about 1 to
about 10, and about 3 about 8 kg/mol.
[0052] In one or more embodiments, the adducts contain from about 5
to about 25 double bonds per 100 carbon atoms. In other
embodiments, the adduct contains from about 6 to about 20 double
bonds per 100 carbon atoms, in other embodiments from about 7 to
about 18 double bonds per 100 carbon atoms, and in other
embodiments, the adduct contains from about 10 to about 16 double
bonds per 100 carbon atoms.
[0053] In another embodiment, the adducts have about 0.1 to about
33 weight %, and in another embodiment, from about 1 to about 10
weight percent of pendant anhydride groups, based on the adduct,
and still further about 2 to about 10% by weight. In another
embodiment, the adducts have from about 2 to about 4 weight %
pendant anhydride groups.
[0054] In another embodiment, the adducts have from 51% to 99% cis
content, in another embodiment from about 52% to about 85% cis
content, in another embodiment from about 52% to about 80% cis
content, in another embodiment from about 52% to about 75% cis
content, in another embodiment from about 52% to about 70% cis
content in still another embodiment from about 52% to about 65% cis
content, and in another embodiment from 53% to 65% cis content, and
in another embodiment from 53% to 60% cis content, in still another
embodiment from about 55% to about 75% cis content, in another
embodiment from about 55% to about 70% cis content, in another
embodiment greater than about 55% cis content, in another
embodiment greater than about 60% cis content, in another
embodiment greater than about 65% cis content, and in another
embodiment greater than about 70% cis content.
[0055] In another embodiment, the adduct may have a melting point
of less than 40.degree. C., in another embodiment less than about
30.degree. C., in another embodiment less than about 25.degree. C.,
and in another embodiment less than about 10.degree. C. In another
embodiment, the polymer has a melting point in the range of about
0.degree. C. to about 25.degree. C., in another embodiment from
about 5.degree. C. to about 20.degree. C.
[0056] In another embodiment, the adducts have a crystallinity of
less than 10%, in another embodiment less than about 8%, in another
embodiment less than about 7%, in another embodiment less than
about 5%, and in another embodiment less than about 3%.
[0057] The adducts may be prepared by reacting the metathesis
polymers with from about 0.1 to about 50 weight % unsaturated
diacid anhydride, based on the weight of the polymer. The reaction
may be any technique that will cause reaction of the metathesis
polymer with the unsaturated diacid anhydride to occur.
[0058] Exemplary of the techniques that may be used in reacting the
metathesis polymer with the unsaturated diacid anhydride are the
ene reaction process and the radical addition process. These
techniques are described as follow: The ene reaction is a
site-specific organic chemistry reaction between an alkene
containing an allylic hydrogen (the ene) and a compound containing
an activated double bond (the enophile). The reactive ene double
bond can be present on a small molecule such as a monomer, or on a
polymer (backbone or pendant group). The reaction is usually
catalyzed by thermal energy or by the presence of a Lewis acid such
as BF.sub.3, AlCl.sub.3. The product of the ene reaction is a
substituted alkene or an adduct with the double bond shifted one
carbon to the allylic position.
[0059] The ene reaction is performed by mixing or blending an
unsaturated metathesis polymer, neat or in solution, with an
unsaturated diacid anhydride (about 0.1-50 weight percent based on
polymer). The reaction contents are heated in a reaction vessel or
in an extruder at a temperature range of about 160-240.degree. C.
for about 0.1-24 hours or until spectroscopic analyses indicated
the desired level of adduct has been formed.
[0060] Alternatively, the adduct can be prepared by employing a
radical initiator such as di-tert-butyl peroxide, dicumyl peroxide
.alpha.,.alpha.-azoisobutyronitrile (AIBN), and tert-butyl
peroxybenzoate, in combination with a metathesis polymer, neat or
in solution, and an unsaturated diacid anhydride (about 0.1 to
about 50 weight percent based on the polymer). The reaction may be
carried out at a temperature ranging from about 50 to about
150.degree. C. Optionally, a radical inhibitor or an antioxidant
may be employed.
[0061] Examples of other suitable radical initiators are well
known. These include one, or a mixture of diacyl peroxides such as
benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, octanoyl peroxide
and lauroyl peroxide, dialkyl peroxides such as di-t-butyl
peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane-3, dicumyl
peroxide and .alpha.,.alpha.'bis(t-butyl
peroxy-m-isopropyl)benzene; peroxy esters such as t-butyl
perbenzoate, t-butyl peroxy-m-isopropyl)benzene; peroxy esters such
as t-butyl perbenzoate, t-butyl peracetate, di-t-butyl perphthalate
and 2,5-dimethyl-2,5-di(benzoylperoxy)hexane; ketone peroxides such
as methyl ethyl ketone peroxide and cyclohexanone peroxide;
hydroperoxides such as di-t-butyl hydroperoxide, cumene
hydroperoxide, .alpha.-phenylethyl hydroperoxide and cyclohexenyl
hydroperoxide; and peroxy ketals such as
1,1-bis(t-butylperoxy)cyclohexane and
1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane. The amounts
typically used range from about 0.001-0.5 weight %.
[0062] Examples of useful unsaturated anhydrides include those
having the formula shown below.
##STR00009##
[0063] wherein R.sub.1, and R.sub.2 are the same or different, and
are selected from hydrogen or a monovalent organic group. In one or
more embodiments, the monovalent organic groups may include
hydrocarbyl groups or substituted hydrocarbyl groups such as, but
not limited to, alkyl, cycloalkyl, substituted cycloalkyl, aryl,
substituted aryl, aralkyl, alkaryl, with each group having from 1
to 30 carbon atoms. The hydrocarbyl groups may contain heteroatoms
such as, but not limited to, nitrogen, boron, oxygen, silicon,
sulfur, and phosphorus atoms.
[0064] Such unsaturated diacid anhydrides include, but are not
limited to, maleic anhydride, citraconic anhydride, itaconic
anhydride, glutaconic anhydride, crotonic anhydride,
3,4,5,6-tetrahydrophthalic anhydride, 2,3-dimethylmaleic anhydride,
bromomaleic anhydride, chloromaleic anhydride, dibromomaleic
anhydride, and dichloromaleic anhydride. In one embodiment, the
diacid anhydride is maleic anhydride.
[0065] While certain representative embodiments and details have
been shown for the purpose of illustrating the invention, it will
be apparent to those skilled in the art that various changes and
modifications may be made therein without departing from the spirit
or the scope of the invention.
* * * * *